Non-isocyanate polyurethane foam joint mixture and preparation process thereof

Abstract

The invention discloses a non-isocyanate polyurethane foam joint mixture and a preparation process thereof. The non-isocyanate polyurethane foam joint mixture comprises the following components in parts by weight: 60-80 parts of modified carbonate, 70-90 parts of a cross-linking agent, 10-20 parts of epoxy resin, 6-10 parts of a catalyst, 5-7 parts of a flame retardant and 4-8 parts of a foam stabilizer. According to the non-isocyanate polyurethane foam joint mixture and the preparation process thereof, the raw materials are common, the cost is relatively low, the requirement for equipment is relatively low, the non-isocyanate polyurethane foam joint mixture is suitable for industrial large-scale production, and the whole synthesized non-isocyanate polyurethane foam joint mixture is stable in whole, high in solvent resistance and good in stability. Meanwhile, the chemical resistance, the hydrolysis resistance and the permeability resistance are greatly improved, the original state can be kept for a long time in an external environment, the applicability is wide, and the good use prospect is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of foam sealants, and in particular to a non-isocyanate polyurethane foam sealant and a preparation process thereof. Background Art

[0002] Foam sealant is called foaming agent or foam glue. It is the product of the cross-combination of aerosol technology and polyurethane foam technology. This material is mainly composed of polyurethane prepolymer, foaming agent, catalyst and other components, and is filled in a pressure-resistant aerosol can. When the material is sprayed out of the aerosol can, the foamy polyurethane material will expand rapidly and react with the air or moisture in the substrate it contacts to form foam. The cured foam has multiple effects such as filling, bonding, sealing, heat insulation, and sound absorption. It is an environmentally friendly, energy-saving, and easy-to-use building material.

[0003] Polyurethane foam sealant is a single-component, moisture-curing, multi-purpose polyurethane foam filling elastic sealing material. Also known as polyurethane foam glue, it is an indispensable auxiliary product in the door, window and curtain wall industry. Polyurethane foam sealant is a polyurethane prepolymer, catalyst and gas propellant filled in a pressure-resistant iron aerosol can. During construction, the aerosol colloid is sprayed to the bonding part through a matching glue gun or manual spray tube to complete the molding, foaming, bonding and sealing process in a short time.

[0004] The existing patent authorization number is CN113736418B, and the patent name is a modified one-component polyurethane foam sealant and its preparation method. The invention patent records the modified one-component polyurethane foam sealant, which is made of the following raw materials by weight percentage: 5-18% polyether polyol, 10-25% silicone polymer, 0.4-0.8% main catalyst, 0.05-0.15% auxiliary catalyst, 0.5-2% cross-linking agent, 0.005-0.02% antioxidant, 0.05-0.25% ultraviolet absorber, 1-2% silicone oil 8871, 30-40% chlorinated paraffin, 10-18% polymerized MDI, 8-15% dimethyl ether, 4-15% propane and butane. The present invention can effectively prevent and delay the yellowing of the foam produced by the one-component polyurethane foam sealant by adding silicone polymer, antioxidant and ultraviolet absorber, and can improve the temperature resistance of the foam.

[0005] Although the existing modified one-component polyurethane foam sealant has improved some of its performance through modification, it still has the weak bond structure of traditional polyurethane, and its chemical resistance, hydrolysis resistance and permeability resistance are not high. It is easily deformed and broken when exposed to the air for a long time and affected by the environment, which cannot meet people's needs. For this reason, we have invented a non-isocyanate polyurethane foam sealant and its preparation process. Summary of the invention

[0006] The main purpose of the present invention is to provide a non-isocyanate polyurethane foam sealant and a preparation process thereof, which can effectively solve the problems in the background technology.

[0007] To achieve the above object, the technical solution adopted by the present invention is:

[0008] A non-isocyanate polyurethane foam sealant comprises the following components in parts by weight: 60-80 parts of modified carbonate, 70-90 parts of crosslinking agent, 10-20 parts of epoxy resin, 6-10 parts of catalyst, 5-7 parts of flame retardant and 4-8 parts of foam stabilizer;

[0009] The modified carbonate comprises the following components in parts by weight: 60-70 parts of modified menthane diamine, 1-3 parts of benzyl triethyl ammonium chloride, 2-3 parts of ethylene glycol and 100-120 parts of ethyl acetate.

[0010] The preparation method of the modified menthane diamine is as follows:

[0011] S11, adding a mixed catalyst to menthane diamine, raising the temperature to 100-120° C. under a nitrogen atmosphere, and reacting for 4-5 hours to obtain a mixture;

[0012] S12, let the mixture stand at a temperature of 60-70°C, add sodium hydroxide solution and react for 3-4 hours;

[0013] S13, distilling the reaction product to remove impurities, to obtain modified menthane diamine;

[0014] The weight ratio of the menthane diamine, the mixed catalyst and the sodium hydroxide is 1:9:1.

[0015] Preferably, a non-isocyanate polyurethane foam sealant comprises the following components in parts by weight: 70 parts of modified carbonate, 80 parts of cross-linking agent, 16 parts of epoxy resin, 8 parts of catalyst, 7 parts of flame retardant and 7 parts of foam stabilizer.

[0016] Preferably, the cross-linking agent includes an amine compound, the catalyst includes dimorpholine diethyl ether, the flame retardant is one of triphosphate, dimethyl methyl phosphate and chlorinated paraffin, and the foam stabilizer is a mixture of an organosilicon polyurethane foam stabilizer and a foam stabilizer and a foam leveler in a weight ratio of 2:3.

[0017] Preferably, the preparation method of the modified carbonate is as follows:

[0018] S21, adding modified menthane diamine, benzyl triethylammonium chloride and ethylene glycol into a high pressure reactor and stirring;

[0019] S22, ventilating the high-pressure reactor using carbon dioxide gas;

[0020] S23, continuously charging carbon dioxide gas into the high-pressure reactor to increase the pressure, and then stirring and heating the reactor for reaction;

[0021] S24, exhausting the gas, and dissolving the reaction product in ethyl acetate for extraction to obtain modified carbonate.

[0022] Preferably, the high-pressure reactor condensation device is started during the closed stirring in step S21 and the ventilation in step S22, and the temperature of the high-pressure reactor is controlled to be 20-30°C.

[0023] Preferably, in step S23, the pressure is increased to 1 MPa, the temperature is raised to 120-140° C. with stirring, and then the reaction is carried out at a constant temperature and pressure for 5-6 hours.

[0024] Preferably, deionized water at a temperature of 60-70° C. is used for extraction, and the extraction is performed 3-4 times. After the organic phase is collected, it is evaporated under reduced pressure to remove the ethyl acetate solvent and deionized water to obtain the modified carbonate.

[0025] Preferably, the mixed catalyst comprises epichlorohydrin and benzyltriethylammonium chloride, and the weight ratio of epichlorohydrin to benzyltriethylammonium chloride is 150:1.

[0026] Preferably, the amine compound includes Priamine1074.

[0027] Preferably, a method for preparing a non-isocyanate polyurethane foam sealant comprises the following steps:

[0028] (1) adding the crosslinking agent dropwise to the modified carbonate, stirring at room temperature for 0.8-1.2 hours to obtain a mixed solution;

[0029] (2) adding epoxy resin to the mixed solution, stirring and performing ultrasonic reaction for 0.6-0.8 hours to obtain a mixed solution;

[0030] (3) Add the flame retardant, foam stabilizer and catalyst into the mixed solution and stir evenly to obtain a non-isocyanate polyurethane foam sealant.

[0031] Compared with the prior art, the non-isocyanate polyurethane foam sealant and the preparation process thereof of the present invention have the following beneficial effects:

[0032] 1. The non-isocyanate polyurethane foam sealant of the present invention has common raw materials for synthesis, low cost, low requirements for production equipment, is suitable for large-scale industrial production, and has good application prospects;

[0033] 2. A method for preparing a non-isocyanate polyurethane foam sealant of the present invention comprises the following steps: modifying the menthane diamine during production so that the menthane diamine has an epoxy structure, thereby improving the overall stability of the menthane diamine, and then further modifying the menthane diamine so that the epoxy structure is further changed into a carbonate structure, so that the raw materials can be synthesized as a whole during subsequent generation. The non-isocyanate polyurethane foam sealant after synthesis is stable as a whole and has high solvent resistance. At the same time, the chemical resistance, hydrolysis resistance and penetration resistance are greatly improved, and the original state can be maintained for a long time under the external environment. The non-isocyanate polyurethane foam sealant has wide applicability and good prospects for use. DETAILED DESCRIPTION

[0034] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the present invention is further explained below in conjunction with specific implementation methods.

[0035] The sources of raw materials in the specific embodiment of the present invention are as follows: Menthane diamine was purchased from Jiangsu Xinsu New Materials Co., Ltd.; benzyl triethylammonium chloride was purchased from Shandong Qiyun Chemical Technology Co., Ltd., epichlorohydrin was purchased from Shandong Hengshuo Chemical Co., Ltd., and Priamine 1074 was purchased from Guangzhou Si Tuyuan Chemical Co., Ltd.

[0036] Example 1

[0037] Preparation of a non-isocyanate polyurethane foam sealant:

[0038] (1) 60 g of modified menthane diamine, 536.5 g of epichlorohydrin and 3.5 g of benzyl triethylammonium chloride were heated to 110° C. under a nitrogen atmosphere and reacted for 5 hours to obtain a mixture;

[0039] (2) Allow the mixture to stand at 60°C, add 60 g of sodium hydroxide solution and react for 3 hours;

[0040] (3) distilling the reaction product to remove impurities to obtain modified menthane diamine;

[0041] (4) Add 60 g of modified menthane diamine, 2 g of benzyl triethylammonium chloride and 3 g of ethylene glycol into a closed autoclave and stir. During stirring, start the autoclave condensation device and control the autoclave temperature to 25° C.

[0042] (5) Ventilate the autoclave with carbon dioxide gas for 5 times. During the whole ventilation process, start the autoclave condensation device and control the autoclave temperature to 25°C.

[0043] (6) Continuously charging carbon dioxide gas into the autoclave to increase the pressure, and then stirring and heating the autoclave to react, raising the pressure to 1 MPa, stirring and heating to 130° C., and then reacting at a constant temperature and pressure for 6 hours;

[0044] (7) Exhaust the gas and dissolve the reaction product in 100 g of ethyl acetate for extraction. Deionized water at a temperature of 65° C. is used for extraction 4 times. The organic phase is collected and evaporated under reduced pressure to remove the ethyl acetate solvent and deionized water to obtain a modified carbonate;

[0045] (8) 72 g of Priamine 1074 was added dropwise to 61 g of modified carbonate, and stirred at room temperature for 1.0 hour to obtain a mixed solution;

[0046] (9) adding 15 g of epoxy resin to the mixed solution, stirring and ultrasonically reacting for 0.6 h to obtain a mixed solution;

[0047] (10) Add 5 g of dimethyl methyl phosphate, 5 g of a mixture of a silicone polyurethane foam stabilizer and a foam stabilizer and a foam leveler in a ratio of 2:3, and 6 g of dimorpholine diethyl ether to the mixed solution and stir evenly to obtain a non-isocyanate polyurethane foam sealant.

[0048] Example 2

[0049] Preparation of a non-isocyanate polyurethane foam sealant:

[0050] (1) 60 g of modified menthane diamine, 536.5 g of epichlorohydrin and 3.5 g of benzyl triethylammonium chloride were heated to 110° C. under a nitrogen atmosphere and reacted for 5 hours to obtain a mixture;

[0051] (2) Allow the mixture to stand at 60°C, add 60 g of sodium hydroxide solution and react for 3 hours;

[0052] (3) distilling the reaction product to remove impurities to obtain modified menthane diamine;

[0053] (4) Add 60 g of modified menthane diamine, 2 g of benzyl triethylammonium chloride and 3 g of ethylene glycol into a closed autoclave and stir. During stirring, start the autoclave condensation device and control the autoclave temperature to 25° C.

[0054] (5) Ventilate the autoclave with carbon dioxide gas for 5 times. During the whole ventilation process, start the autoclave condensation device and control the autoclave temperature to 25°C.

[0055] (6) Continuously charging carbon dioxide gas into the autoclave to increase the pressure, and then stirring and heating the autoclave to react, raising the pressure to 1 MPa, stirring and heating to 130° C., and then reacting at a constant temperature and pressure for 6 hours;

[0056] (7) Exhaust the gas and dissolve the reaction product in 100 g of ethyl acetate for extraction. Deionized water at a temperature of 65° C. is used for extraction 4 times. The organic phase is collected and evaporated under reduced pressure to remove the ethyl acetate solvent and deionized water to obtain a modified carbonate;

[0057] (8) 81 g of Priamine 1074 was added dropwise to 71 g of modified carbonate, and stirred at room temperature for 1.1 hours to obtain a mixed solution;

[0058] (9) adding 15 g of epoxy resin to the mixed solution, stirring and ultrasonically reacting for 0.8 h to obtain a mixed solution;

[0059] (10) Add 6 g of dimethyl methyl phosphate, 8 g of a mixture of a silicone polyurethane foam stabilizer and a foam stabilizer and a foam leveler in a ratio of 2:3, and 8 g of dimorpholine diethyl ether to the mixed solution and stir evenly to obtain a non-isocyanate polyurethane foam sealant.

[0060] The following components are included by weight: 70 parts of modified carbonate, 80 parts of crosslinking agent, 16 parts of epoxy resin, 8 parts of catalyst, 7 parts of flame retardant and 7 parts of foam stabilizer

[0061] Modified carbonate 60-80 parts, crosslinking agent 70-90 parts, epoxy resin 10-20 parts, catalyst 6-10 parts, flame retardant 5-7 parts and foam stabilizer 4-8 parts

[0062] Example 3

[0063] Preparation of a non-isocyanate polyurethane foam sealant:

[0064] (1) 60 g of modified menthane diamine, 536.5 g of epichlorohydrin and 3.5 g of benzyl triethylammonium chloride were heated to 110° C. under a nitrogen atmosphere and reacted for 5 hours to obtain a mixture;

[0065] (2) Allow the mixture to stand at 60°C, add 60 g of sodium hydroxide solution and react for 3 hours;

[0066] (3) distilling the reaction product to remove impurities to obtain modified menthane diamine;

[0067] (4) Add 60 g of modified menthane diamine, 2 g of benzyl triethylammonium chloride and 3 g of ethylene glycol into a closed autoclave and stir. During stirring, start the autoclave condensation device and control the autoclave temperature to 25° C.

[0068] (5) Ventilate the autoclave with carbon dioxide gas for 5 times. During the whole ventilation process, start the autoclave condensation device and control the autoclave temperature to 25°C.

[0069] (6) Continuously charging carbon dioxide gas into the autoclave to increase the pressure, and then stirring and heating the autoclave to react, raising the pressure to 1 MPa, stirring and heating to 130° C., and then reacting at a constant temperature and pressure for 6 hours;

[0070] (7) Exhaust the gas and dissolve the reaction product in 100 g of ethyl acetate for extraction. Deionized water at a temperature of 65° C. is used for extraction 4 times. The organic phase is collected and evaporated under reduced pressure to remove the ethyl acetate solvent and deionized water to obtain a modified carbonate;

[0071] (8) 88 g of Priamine 1074 was added dropwise to 79 g of modified carbonate, and stirred at room temperature for 1.2 hours to obtain a mixed solution;

[0072] (9) adding 19 g of epoxy resin to the mixed solution, stirring and ultrasonically reacting for 0.8 h to obtain a mixed solution;

[0073] (10) 7 g of dimethyl methyl phosphate, 8 g of a mixture of a silicone polyurethane foam stabilizer and a foam stabilizer and a foam leveler in a ratio of 2:3, and 10 g of dimorpholine diethyl ether were added to the mixed solution and stirred evenly to obtain a non-isocyanate polyurethane foam sealant.

[0074] Comparative Example:

[0075] A modified one-component polyurethane foam sealant, the formula is as follows:

[0076] Polyether polyol 65.9g, dihydroxy polydimethylsiloxane 84.8g, terminal hydroxyl polyether modified polysiloxane 33g, DMDEE 2.8g, stannous octoate 0.7g, vinyl trisbutyl ketoxime silane 7g, antioxidant 30N 0.05g, UV NP 30.45g, silicone oil 887114.1g, chlorinated paraffin 262.2g, polymerized MDI 122g, dimethyl ether 72g, and propane 85g.

[0077] The preparation method is as follows:

[0078] Weigh various raw materials according to the above raw material ratio;

[0079] The weighed polyether polyol, dihydroxy polydimethylsiloxane, terminal hydroxyl polyether modified polysiloxane, DMDEE, stannous octoate, vinyl trisbutyl ketoxime silane, antioxidant 30N, UVNP3, silicone oil 8871 and chlorinated paraffin were sequentially added into a 1L mixer with a stirring device, and mixed and stirred for 2 hours to obtain a mixture;

[0080] Add the mixture into an aerosol can, then add polymerized MDI and seal the can; then use a special filling machine to fill in dimethyl ether and propane and butane, press the cap and shake for 60 times, and place it at room temperature for 48 hours to obtain a modified one-component polyurethane foam sealant.

[0081] Performance Testing

[0082] Sample preparation: The products produced in the examples and comparative examples were introduced into a mold for free foaming and aged in a constant temperature box at 40°C for 4 hours. The surface crust was then removed and the samples were cut into 70 mm in length, 10 mm in width and 10 mm in thickness.

[0083] The flame retardant properties of the polyurethane foams in the examples and comparative examples were tested with reference to GB / T2406.2-2009 “Determination of combustion behavior of plastics by oxygen index Part 2: Room temperature test”.

[0084] The compressive strength of the polyurethane foam in the examples and comparative examples was tested with reference to GB / T8813-2008 "Determination of compression properties of rigid foam plastics";

[0085] The samples were baked at 150°C for 48 hours, the dimensions were measured, and the shrinkage was calculated;

[0086] The performance parameter table is as follows:

[0087] High temperature shrinkage (%) Flame retardant grade Compression strength(kPa) Tensile strength(kPa) Example 1 7％ B2 1.61 0.79 Example 2 6％ B2 1.64 0.84 Example 3 7％ B2 1.67 0.86 Comparative Example 9％ B3 1.57 0.42

[0088] It can be seen from the data in the above table that the preparation method of the non-isocyanate polyurethane foam sealant of the present invention has relatively common raw materials for synthesis, and has relatively low cost, low requirements for production equipment, is suitable for industrial large-scale production, and has good application prospects;

[0089] The invention discloses a method for preparing a non-isocyanate polyurethane foam sealant. During production, the menthane diamine is modified so that the menthane diamine has an epoxy structure, thereby improving the overall stability of the menthane diamine. The menthane diamine is then further modified so that the epoxy structure is further changed into a carbonate structure, so that the raw materials can be synthesized as a whole during subsequent generation. The synthesized non-isocyanate polyurethane foam sealant is overall stable and has high solvent resistance. At the same time, the chemical resistance, hydrolysis resistance and penetration resistance are greatly improved, and the original state can be maintained for a long time under the external environment. The non-isocyanate polyurethane foam sealant has wide applicability and good use prospects.

[0090] The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A non-isocyanate polyurethane foam sealant, characterized in that: The composition comprises the following components by weight: 60-80 parts of modified carbonate, 70-90 parts of crosslinking agent, 10-20 parts of epoxy resin, 6-10 parts of catalyst, 5-7 parts of flame retardant and 4-8 parts of foam stabilizer; The modified carbonate comprises the following components in parts by weight: 60-70 parts of modified menthane diamine, 1-3 parts of benzyl triethyl ammonium chloride, 2-3 parts of ethylene glycol and 100-120 parts of ethyl acetate. The preparation method of the modified menthane diamine is as follows: S11, adding a mixed catalyst to menthane diamine, raising the temperature to 100-120° C. under a nitrogen atmosphere, and reacting for 4-5 hours to obtain a mixture; S12, let the mixture stand at a temperature of 60-70°C, add sodium hydroxide solution and react for 3-4 hours; S13, distilling the reaction product to remove impurities, to obtain modified menthane diamine; The weight ratio of the menthane diamine, the mixed catalyst and the sodium hydroxide is 1:9:

1.

2. The non-isocyanate polyurethane foam sealant according to claim 1, characterized in that: The composition comprises the following components in parts by weight: 70 parts of modified carbonate, 80 parts of cross-linking agent, 16 parts of epoxy resin, 8 parts of catalyst, 7 parts of flame retardant and 7 parts of foam stabilizer.

3. The non-isocyanate polyurethane foam sealant according to claim 1, characterized in that: The catalyst includes dimorpholine diethyl ether, the flame retardant is one of triphosphate, dimethyl methyl phosphate and chlorinated paraffin, and the foam stabilizer is a mixture of an organic silicon polyurethane foam stabilizer and a foam stabilizer and a foam leveler in a weight ratio of 2:

3.

4. The non-isocyanate polyurethane foam sealant according to claim 1, characterized in that: The preparation method of the modified carbonate is as follows: S21, adding modified menthane diamine, benzyl triethylammonium chloride and ethylene glycol into a high pressure reactor and stirring; S22, ventilating the high-pressure reactor using carbon dioxide gas; S23, continuously charging carbon dioxide gas into the high-pressure reactor to increase the pressure, and then stirring and heating the reactor for reaction; S24, exhausting the gas, and dissolving the reaction product in ethyl acetate for extraction to obtain modified carbonate.

5. The non-isocyanate polyurethane foam sealant according to claim 1, characterized in that: During the closed stirring in step S21 and the ventilation in step S22, the high-pressure reactor condensation device is started to control the temperature of the high-pressure reactor to 20-30°C.

6. The non-isocyanate polyurethane foam sealant according to claim 1, characterized in that: In step S23, the pressure is increased to 1 MPa, the temperature is raised to 120-140° C. with stirring, and then the reaction is carried out at a constant temperature and pressure for 5-6 hours.

7. The non-isocyanate polyurethane foam sealant according to claim 1, characterized in that: Deionized water at a temperature of 60-70° C. is used for extraction, and the extraction is performed 3-4 times. The organic phase is collected and evaporated under reduced pressure to remove the ethyl acetate solvent and the deionized water, thereby obtaining a modified carbonate.

8. The non-isocyanate polyurethane foam sealant according to claim 1, characterized in that: The mixed catalyst comprises epichlorohydrin and benzyltriethylammonium chloride, and the weight ratio of epichlorohydrin to benzyltriethylammonium chloride is 150:

1.

9. The non-isocyanate polyurethane foam sealant according to claim 1, characterized in that: The amine compounds include Priamine1074.

10. The method for preparing a non-isocyanate polyurethane foam sealant according to any one of claims 1 to 9, characterized in that: The following steps are involved: (1) adding the crosslinking agent dropwise to the modified carbonate, stirring at room temperature for 0.8-1.2 hours to obtain a mixed solution; (2) adding epoxy resin to the mixed solution, stirring and performing ultrasonic reaction for 0.6-0.8 hours to obtain a mixed solution; (3) Add the flame retardant, foam stabilizer and catalyst into the mixed solution and stir evenly to obtain a non-isocyanate polyurethane foam sealant.